Catalyst complex with carbene ligand
Catalytic complexes including a metal atom having anionic ligands, at least one nucleophilic carbene ligand, and an alkylidene, vinylidene, or allenylidene ligand. The complexes are highly stable to air, moisture and thermal degradation. The complexes are designed to efficiently carry out a variety of olefin metathesis reactions.
1. A catalytic complex of the formula:
wherein M is Ru;
R and R 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl each R and R 1 optionally being substituted with halogen, C 1 -C 10 alkyl groups, C 1 -C 10 alkoxy groups, aryl groups, or with a functional group selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, amide, amine, imine, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen, wherein any R or R 1 optionally include structural isomers, cyclic or polycyclic isomers, and multiply unsaturated variants of said isomers;
X and X 1 are independently selected from the group consisting of anionic ligands;
L is selected from the group consisting of phosphines, sulfonated phosphines, phosphites, phosphinites, phosphonites, arsine, stibine, imines, ethers, amines, amides, sulfoxides, carbonyls, carboxyls, nitrosyls, pyridines, and thioethers; and
L 1 is of the formula:
wherein Y and Y 1 are each independently an aryl group substituted with halogen, C 1 -C 5 alkyl groups, or C 1 -C 5 alkoxy groups; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with halogen, C 1 -C 5 alkyl groups, or C 1 -C 5 alkoxy groups.
2. The catalytic complex of claim 1 , wherein R 1 is a C 1 -C 20 alkyl, where the C 1 -C 20 alkyl is substituted with a functional group selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, amide, amine, imine, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
3. The catalytic complex of claim 1 , wherein R 1 is a C 1 -C 20 alkyl, where the C 1 -C 20 alkyl is substituted with a functional group selected from thioether and imine.
4. The catalytic complex of claim 3 , wherein R 1 is a cyclic isomer.
5. The catalytic complex of claim 4 , wherein the cyclic isomer is a multiply unsaturated variant of said cyclic isomer.
6. The catalytic complex of claim 5 , wherein R is selected from the group consisting of hydrogen, C 1 -C 20 alkyl, and aryl; L is selected from the group consisting of phosphines, phosphites, phosphinites, phosphonites, and pyridines; Y and Y 1 are each independently an aryl group substituted with C 1 -C 5 alkyl groups; and Z and Z 1 are independently selected from the group consisting of hydrogen and C 1 -C 20 alkyl.
7. The catalytic complex of claim 5 , wherein R is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and phenyl; X and X 1 are each halide, CF 3 CO 2 , CH 3 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, brosylate or trifluoromethanesulfonate; L is selected from the group consisting of phosphines, phosphites, phosphinites, and phosphonites; Y and Y 1 are each independently an aryl group substituted with C 1 -C 5 alkyl groups; and Z and Z 1 are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and sec-butyl.
8. The catalytic complex of claim 5 , wherein R is hydrogen; X and X 1 are chloride; Y and Y 1 are each 2,4,6-trimethylphenyl; L is selected from phosphines; and Z and Z 1 are independently hydrogen or methyl.
9. The catalytic complex of claim 8 , wherein L is selected from trimethylphosphine, triphenylphosphine, triisopropylphosphine, tricyclohexylphosphine, and tricyclopentylphosphine.
10. The catalytic complex of claim 5 , wherein R is hydrogen; X and X 1 are chloride; Y and Y 1 are each 2,6-diisopropylphenyl; L is selected from phosphines; and Z and Z 1 are independently hydrogen or methyl.
11. The catalytic complex of claim 10 , wherein L is selected from trimethylphosphine, triphenylphosphine, triisopropylphosphine, tricyclohexylphosphine, and tricyclopentylphosphine.
12. The catalytic complex of claim 1 , wherein R 1 is a C 1 -C 20 alkyl, where the C 1 -C 20 alkyl is substituted with a C 1 -C 10 alkoxy group.
13. The catalytic complex of claim 12 , wherein R 1 is a cyclic isomer.
14. The catalytic complex of claim 13 , wherein the cyclic isomer is a multiply unsaturated variant of said cyclic isomer.
15. The catalytic complex of claim 14 , wherein R is selected from the group consisting of hydrogen, C 1 -C 20 alkyl, and aryl; L is selected from the group consisting of phosphines, phosphites, phosphinites, phosphonites, and pyridines; Y and Y 1 are each independently an aryl group substituted with C 1 -C 5 alkyl groups; and Z and Z 1 are independently selected from the group consisting of hydrogen and C 1 -C 20 alkyl.
16. The catalytic complex of claim 14 , wherein R is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and phenyl; X and X 1 are each halide, CF 3 CO 2 , CH 3 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, brosylate or trifluoromethanesulfonate; L is selected from the group consisting of phosphines, phosphites, phosphinites, and phosphonites; Y and Y 1 are each independently an aryl group substituted with C 1 -C 5 alkyl groups; and Z and Z 1 are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and sec-butyl.
17. The catalytic complex of claim 14 , wherein R is hydrogen; X and X 1 are chloride; Y and Y 1 are each 2,4,6-trimethylphenyl; L is selected from phosphines; and Z and Z 1 are independently hydrogen or methyl.
18. The catalytic complex of claim 17 , wherein L is selected from trimethylphosphine, triphenylphosphine, triisopropylphosphine, tricyclohexylphosphine, and tricyclopentylphosphine.
19. The catalytic complex of claim 14 , wherein R is hydrogen; X and X 1 are chloride; Y and Y 1 are each 2,6-diisopropylphenyl; L is selected from phosphines; and Z and Z 1 are independently hydrogen or methyl.
20. The catalytic complex of claim 19 , wherein L is selected from trimethylphosphine, triphenylphosphine, triisopropylphosphine, tricyclohexylphosphine, and tricyclopentylphosphine.